KR100512366B1 - Method for Preparing Styrene-Butadienes Latex - Google Patents
Method for Preparing Styrene-Butadienes Latex Download PDFInfo
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- KR100512366B1 KR100512366B1 KR10-2003-0042582A KR20030042582A KR100512366B1 KR 100512366 B1 KR100512366 B1 KR 100512366B1 KR 20030042582 A KR20030042582 A KR 20030042582A KR 100512366 B1 KR100512366 B1 KR 100512366B1
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
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Abstract
본 발명은 종이 코팅용 스티렌-부타디엔계 라텍스의 제조방법에 관한 것으로, 스티렌-부타디엔계 라텍스의 제조방법에 있어서, a) 스티렌-부타디엔계 중합체의 코아 라텍스를 제조하는 단계; b) 상기 코아 라텍스의 외부에 쉘 중합물을 2∼4 중으로 피복시키는 단계; 및 c) 상기 b)단계의 쉘 중합 전환율이 60 내지 95%가 되는 시점에서, 연쇄이동제를 단독으로 첨가하여 라텍스 최외곽층의 겔 함량 및 분자량을 조절하는 단계;를 포함하여 이루어지는 스티렌-부타디엔계 라텍스의 제조방법을 제공한다. 본 발명은 다중 쉘 제조를 위한 원료의 투입이 끝난 후 연쇄이동제를 투입하면 라텍스 입자 최외곽층의 겔 함량 및 분자량을 조절하여 종이 코팅시 필름이 형성되는 속도와 필름이 유지되는 정도를 조절하는 것이 가능하므로 코팅지의 접착력이 매우 우수해지고 잉크건조속도와 투기도가 동시에 향상된다. 또한 라텍스의 화학적, 기계적 안전성이 우수해지므로 종이 코팅시 발생할 수 있는 여러 가지 작업성 문제를 해결할 수 있는 효과가 있다.The present invention relates to a method for producing styrene-butadiene-based latex for paper coating, the method for producing styrene-butadiene-based latex comprising the steps of: a) preparing core latex of styrene-butadiene-based polymer; b) coating the shell polymer with 2 to 4 on the outside of the core latex; And c) adjusting the gel content and molecular weight of the latex outermost layer by adding a chain transfer agent alone when the shell polymerization conversion rate of step b) becomes 60 to 95%. It provides a method for producing latex. According to the present invention, when the chain transfer agent is added after the input of the raw material for the production of the multi-shell, the gel content and the molecular weight of the outermost layer of the latex particles are adjusted to control the rate at which the film is formed and the degree of the film being maintained during paper coating. As a result, the adhesion of coated paper is very good, and the ink drying speed and air permeability are improved simultaneously. In addition, since the chemical and mechanical safety of the latex is excellent, there are effects that can solve various workability problems that may occur when coating the paper.
Description
본 발명은 스티렌-부타디엔계 라텍스의 제조방법에 관한 것이다. 더욱 상세하게, 본 발명은 스티렌-부타디엔계 라텍스는 최외곽층의 겔 함량 및 분자량을 조절함으로써 코팅시 초기 필름 형성을 빠르게 하여 라텍스의 접착 능력을 뛰어나게 하며, 적절한 필름 형성을 유지하여 잉크건조속도가 빠르고 투기도가 높다는 특성을 지니며, 라텍스의 기계적, 화학적 안정성이 탁월하여 종이 코팅에 매우 안정적으로 적용할 수 있는 스티렌-부타디엔계 라텍스의 제조방법에 관한 것이다.The present invention relates to a method for producing styrene-butadiene-based latex. More specifically, in the present invention, the styrene-butadiene-based latex adjusts the gel content and the molecular weight of the outermost layer to accelerate the initial film formation during coating, thereby improving the adhesion ability of the latex, and maintaining the proper film formation to maintain the proper film formation. It has a fast and high air permeability, and excellent mechanical and chemical stability of the latex, and relates to a method for producing a styrene-butadiene-based latex that can be applied very stably to paper coating.
일반적으로 코팅지는 클레이, 탄산칼슘, 알루미늄 히드록사이드(Al(OH)3), 산화티타늄(TiO2) 등의 무기안료를 종이 위에 코팅하여 제조하는데, 상기 무기안료는 접착력이 없으므로 카세인, 전분 등의 천연 바인더(binder)나 스티렌-부타디엔계 라텍스, 폴리비닐 알콜, 아크릴계 라텍스 등의 인조 바인더를 접착제로서 사용하게 된다. 천연바인더에 비해 물성의 조절이 쉬우며 사용이 편리하다는 장점으로 인하여 현재 인조 합성 바인더가 주로 사용되고 있으며, 이중에서도 가격이 저렴하고 성능이 우수한 스티렌-부타디엔계 라텍스가 대표적으로 사용되고 있다. 코팅액 제조시 무기안료와 바인더 이 외에도 분산제나 증점제, 내수화제 등 각종 참가제가 함께 사용된다. 하지만 가장 큰 비중을 차지하고 있는 것은 무기안료와 바인더이며, 균형 잡힌 코팅지 물성을 얻는 방향으로 선택이 이루어져야 한다.In general, coated paper is prepared by coating inorganic pigments such as clay, calcium carbonate, aluminum hydroxide (Al (OH) 3 ), titanium oxide (TiO 2 ) on paper, and the inorganic pigments do not have adhesive force, so casein, starch, etc. Artificial binders such as natural binders, styrene-butadiene-based latexes, polyvinyl alcohols, and acrylic latexes are used as adhesives. Synthetic binders are mainly used due to the advantages of easy control of physical properties and ease of use compared to natural binders, and among them, styrene-butadiene-based latexes, which are inexpensive and have excellent performance, are typically used. In addition to inorganic pigments and binders, coating agents can be used with various additives such as dispersants, thickeners, and water repellents. However, the largest share of inorganic pigments and binders should be chosen to achieve balanced coating properties.
무기안료 중 가장 많이 사용되는 것은 클레이와 탄산칼슘이다. 클레이는 판상형 구조로서 높은 백지광택 및 인쇄광택을 얻을 수 있다는 장점을 가지는 반면 유동성이 떨어지고 바인더 요구량이 많아진다는 단점을 가지고 있으며, 탄산칼슘의 경우, 유동성, 접착력, 잉크수리성, 종이밝기, 불투명성 등에 유리한 반면 칼슘 양이온에 대한 코팅액의 화학적 안정성이 더욱 크게 요구된다는 문제점이 있다.The most common inorganic pigments are clay and calcium carbonate. Clay has the advantage of being able to obtain high gloss and printing gloss as a plate-like structure, but has the disadvantage of low fluidity and high binder demand.In the case of calcium carbonate, fluidity, adhesion, ink repair, paper brightness, opacity, etc. On the other hand, there is a problem that the chemical stability of the coating liquid against calcium cations is required more.
최근, 종이 제조 속도가 점차 높아짐에 따라, 코팅 속도를 높임으로써 생산성 향상과 급증하는 인쇄물의 공급에 대처하려는 움직임 역시 진행되고 있다. 최근의 코팅 속도는 1000~1500m/min 정도의 빠른 수준까지 올라와 있는데, 이렇게 코팅속도를 높이게 되면 코팅시 전단력이 더욱 커지게 되므로, 라텍스의 기계적 안정성이 더욱 중요해 진다.In recent years, as the paper manufacturing speed is gradually increased, the movement to cope with the increase in the productivity and supply of the rapidly increasing printing by increasing the coating speed is also progressing. The recent coating speed is up to a high level of 1000 ~ 1500m / min, this increase in the coating speed is greater shear force during coating, mechanical stability of the latex becomes more important.
또한, 원가절감과 함께 탄산칼슘의 성능 향상으로 인하여 점점 탄산칼슘의 사용량이 증가되고 있으므로 이와 함께 라텍스의 화학적 안정성 또한 높은 수준으로 요구되어 지고 있다.In addition, due to the cost reduction and the improvement of the performance of calcium carbonate, the amount of calcium carbonate is gradually increased and at the same time, the chemical stability of the latex is also required to a high level.
라텍스의 안정성은 화학적, 기계적, 열적 안정성으로 구별할 수 있으며, 높은 수준의 안정성을 확보하기 위해서는 상기한 3가지의 안정성이 모두 확보되어야 한다. Stability of the latex can be distinguished by chemical, mechanical and thermal stability, all three of the above stability must be secured in order to ensure a high level of stability.
종이 품질의 향상과 코팅지 제조시 원가절감을 위하여 최근 바인더의 함량을 감소시키는 경향이 강해지면서, 바인더의 접착력 향상에 대한 요구가 심화되고 있다. 이와 더불어 빠른 인쇄속도로 인하여 잉크건조속도의 향상에 대한 요구도 높아지고 있는 바, 이 두 가지 물성을 모두 향상시켜야만 최근의 코팅지 제조 및 인쇄공정에 알맞은 코팅지를 얻을 수 있을 것이다.In recent years, as the tendency to reduce the content of the binder for the purpose of improving paper quality and cost reduction in manufacturing coated paper, there is a growing demand for improving the adhesive strength of the binder. In addition, due to the high printing speed, the demand for improving the ink drying speed is also increasing. Therefore, it is necessary to improve both properties to obtain a coating paper suitable for the recent coating paper manufacturing and printing process.
코팅지의 접착력은 코팅액에 투입되는 바인더가 건조 공정을 거치며 필름을 형성하면서 발현되는 것으로 필름이 잘 형성될수록 접착력은 증가하지만 코팅층내의 기공이 감소하면서 잉크건조속도가 저하되는 결과를 낳는다. 따라서 접착력과 잉크건조속도는 어느 정도 반비례하는 물성으로 라텍스의 유리전이온도 등의 단순한 조절로는 이 두 가지 물성을 모두 향상시키는 것이 매우 어렵다.The adhesive force of the coated paper is expressed as the binder is put into the coating liquid through a drying process to form a film. As the film is formed well, the adhesive force increases, but the pore in the coating layer decreases, resulting in a decrease in ink drying speed. Therefore, adhesion and ink drying speed are somewhat inversely proportional, and it is very difficult to improve both properties by simple control such as latex glass transition temperature.
이에 본 발명자들은 스티렌-부타디엔계 라텍스의 접착력과 잉크건조속도, 투기도 및 라텍스 안정성을 동시에 향상시키기 위하여 연구한 결과, 다중 코아-쉘 구조 중 쉘 최외곽층의 겔 함량 및 분자량을 조절함으로써 상기 목적을 달성할 수 있음을 발견하였다. 즉, 코아를 쉘로 피복하기 위하여 중합하는 과정에서 연쇄이동제를 쉘 제조를 위한 단량체와 같이 투입하는 일반적인 겔 함량 및 분자량 조절 방법을 이용함과 동시에 이들 단량체의 투입이 끝난 후 어느 정도의 전환율에서 일정시간 동안 일정량의 연쇄이동제를 단독으로 투입함으로써 다중 쉘의 최외곽층의 겔 함량 및 분자량을 조절할 경우 종이 코팅용 라텍스의 접착력과 잉크건조속도, 투기도 및 라텍스의 안정성을 동시에 향상시킬 수 있다는 것을 발견하고, 이 발견에 기초하여 본 발명을 완성하게 되었다.The present inventors have studied to improve the adhesion of the styrene-butadiene-based latex, the ink drying speed, air permeability and latex stability at the same time, by controlling the gel content and molecular weight of the shell outermost layer of the multi-coa-shell structure It was found that can be achieved. In other words, in order to coat the core with the shell, a general gel content and molecular weight adjustment method is used in which a chain transfer agent is added together with the monomer for shell preparation in the process of polymerization, and at the time of conversion at a certain conversion rate after the completion of the addition of these monomers. By controlling the gel content and molecular weight of the outermost layer of multiple shells by injecting a certain amount of chain transfer agent alone, it was found that the adhesive strength, ink drying speed, air permeability and stability of latex for paper coating can be improved simultaneously. Based on this finding, the present invention has been completed.
상기와 같은 문제점을 해결하기 위하여, 본 발명은 스티렌-부타디엔계 라텍스를 제조함에 있어서 우수한 접착력을 가짐과 동시에 잉크건조속도 및 라텍스의 안정성을 동시에 향상시키는 것을 목적으로 한다.In order to solve the above problems, an object of the present invention is to have an excellent adhesion in the production of styrene-butadiene-based latex and at the same time improve the ink drying speed and stability of the latex.
본 발명의 상기 목적 및 기타 목적들은 하기 설명되는 본 발명에 의하여 모두 달성될 수 있다.The above and other objects of the present invention can be achieved by the present invention described below.
상기 목적을 달성하기 위하여, 본 발명은 스티렌-부타디엔계 라텍스의 제조방법에 있어서,In order to achieve the above object, the present invention provides a method for producing a styrene-butadiene-based latex,
a) 스티렌-부타디엔계 중합체의 코아 라텍스를 제조하는 단계;a) preparing a core latex of styrene-butadiene-based polymer;
b) 상기 코아 라텍스의 외부에 쉘 중합물을 다중으로 피복시키는 단계; 및b) multiple coating of the shell polymer on the exterior of the core latex; And
c) 상기 b)단계의 쉘 중합 전환율이 60 내지 95%가 되는 시점에서, 연쇄이동제를 단독으로 첨가하여 라텍스 최외곽층의 겔 함량 및 분자량을 조절하는 단계;c) adjusting the gel content and molecular weight of the latex outermost layer by adding a chain transfer agent alone when the shell polymerization conversion rate of step b) becomes 60 to 95%;
를 포함하여 이루어지는 스티렌-부타디엔계 라텍스의 제조방법을 제공한다.It provides a method for producing a styrene-butadiene-based latex comprising a.
상기 코아 라텍스는 스티렌, 1,3-부타디엔, 에틸렌성 불포화 산 단량체, 시안화 비닐계 단량체, 이들과 공중합 가능한 단량체, 및 연쇄이동제를 포함하여 이루어지는 코아 조성물을 유화중합하여 제조된다.The core latex is prepared by emulsion polymerization of a core composition comprising styrene, 1,3-butadiene, an ethylenically unsaturated acid monomer, a vinyl cyanide monomer, a monomer copolymerizable with these, and a chain transfer agent.
상기 코아 조성물은 스티렌 35 내지 90 중량부, 1,3-부타디엔 10 내지 55 중량부, 에틸렌성 불포화 산 단량체 1 내지 18 중량부, 시안화 비닐계 단량체 0.5 내지 15 중량부, 공중합 가능한 단량체 1 내지 25 중량부 및 연쇄이동제 0.1 내지 1.0 중량부를 포함하여 이루어진다.The core composition may include 35 to 90 parts by weight of styrene, 10 to 55 parts by weight of 1,3-butadiene, 1 to 18 parts by weight of ethylenically unsaturated acid monomer, 0.5 to 15 parts by weight of vinyl cyanide monomer, and 1 to 25 parts by weight of copolymerizable monomer. And 0.1 to 1.0 parts by weight of the chain transfer agent.
상기 쉘 중합물은 스티렌, 1,3-부타디엔, 에틸렌성 불포화 산 단량체, 시안화 비닐계 단량체, 이들과 공중합 가능한 단량체 및 연쇄이동제를 포함하여 이루어지는 쉘 조성물을 유화중합하여 제조된다.The shell polymer is prepared by emulsion polymerization of a shell composition comprising styrene, 1,3-butadiene, an ethylenically unsaturated acid monomer, a vinyl cyanide monomer, a monomer copolymerizable with these, and a chain transfer agent.
상기 쉘 조성물은 스티렌 30 내지 80 중량부, 1,3-부타디엔 10 내지 70 중량부, 에틸렌성 불포화 산 단량체 0.5 내지 18 중량부, 시안화 비닐계 단량체 1.0 내지 20 중량부, 공중합 가능한 단량체 1.0 내지 20 중량부, 및 연쇄이동제 0.1 내지 5.0 중량부를 포함하여 이루어진다.The shell composition is 30 to 80 parts by weight of styrene, 10 to 70 parts by weight of 1,3-butadiene, 0.5 to 18 parts by weight of ethylenically unsaturated acid monomer, 1.0 to 20 parts by weight of vinyl cyanide monomer, 1.0 to 20 parts by weight of copolymerizable monomer And 0.1 to 5.0 parts by weight of the chain transfer agent.
상기 연쇄이동제는 탄소원자수가 7 ~ 16개인 머캅탄일 수 있다. 상기 연쇄이동제의 사용량은 0.05 ~ 5.0 중량부일 수 있다.The chain transfer agent may be mercaptan having 7 to 16 carbon atoms. The amount of the chain transfer agent may be 0.05 to 5.0 parts by weight.
상기 에틸렌성 불포화 산 단량체는 메타크릴산, 아크릴산, 이타곤산, 크로톤산, 푸루말산, 및 말레인산으로 이루어진 군으로부터 1종 이상 선택되는 불포화카르복실 산; 또는 이타콘산 모노에틸 에스테르, 푸마르산 모노부틸 에스테르, 및 말레산 모노부틸 에스테르로 이루어진 군으로부터 1종 이상 선택되는 1개 이상의 카르복실기를 갖는 불포화 폴리카르복실산 알킬 에스테르일 수 있다.The ethylenically unsaturated acid monomer may be selected from the group consisting of at least one unsaturated carboxylic acid selected from the group consisting of methacrylic acid, acrylic acid, itaconic acid, crotonic acid, fururic acid, and maleic acid; Or unsaturated polycarboxylic acid alkyl esters having at least one carboxyl group selected from the group consisting of itaconic acid monoethyl ester, fumaric acid monobutyl ester, and maleic acid monobutyl ester.
상기 시안화 비닐계 단량체는 아크릴로니트릴 또는 메타크릴로니트릴일 수 있다.The vinyl cyanide monomer may be acrylonitrile or methacrylonitrile.
상기 공중합 가능한 단량체는 메틸아크릴레이트, 메틸메타크릴레이트, 에틸아크릴레이트, 에틸메타크릴레이트, 부틸아크릴레이트, 또는 부틸메타크릴레이트인 불포화 카르복실산 알킬에스테르; β-히드록시에틸 아크릴레이트, β-히드록시프로필 아크릴레이트, 또는 β-히드록시에틸 메타크릴레이트인 불포화카르복실산 히드록시알킬에스테르; 아크릴아미드, 메타크릴아미드, 이타콘아미드, 또는 말레산모노아미드인 불포화 카르복실산 아미드 또는 그 유도체; 및 α-메틸스티렌, 비닐톨루엔, 또는 P-메틸스티렌인 방향족 비닐 단량체;로 이루어진 군으로부터 1 종 이상 선택될 수 있다.The copolymerizable monomer is an unsaturated carboxylic acid alkyl ester which is methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, or butyl methacrylate; unsaturated carboxylic hydroxyalkyl esters which are β-hydroxyethyl acrylate, β-hydroxypropyl acrylate, or β-hydroxyethyl methacrylate; Unsaturated carboxylic acid amides or derivatives thereof which are acrylamide, methacrylamide, itaconeamide, or maleic acid monoamide; And an aromatic vinyl monomer which is α-methylstyrene, vinyltoluene, or P-methylstyrene.
상기 최종 스티렌-부타디엔계 라텍스의 겔 함량이 30 ~ 90 %인 것을 특징으로 하는 스티렌-부타디엔계 라텍스의 제조방법.Method for producing a styrene-butadiene latex, characterized in that the gel content of the final styrene-butadiene-based latex is 30 to 90%.
상기 코아 라텍스의 유리전이온도가 -10 내지 50℃이고, 상기 쉘 중합물의 유리전이온도는 -20 내지 40℃이다.The glass transition temperature of the core latex is -10 to 50 ℃, the glass transition temperature of the shell polymer is -20 to 40 ℃.
상기 a) 단계의 코아 라텍스의 평균입경은 40 내지 90 nm이며, c) 단계에서 제조된 최종 스티렌-부타디엔계 라텍스의 평균입경은 130 내지 260 nm이다.The average particle diameter of the core latex of step a) is 40 to 90 nm, the average particle diameter of the final styrene-butadiene-based latex prepared in step c) is 130 to 260 nm.
또한, 본 발명은 상기 스티렌-부타디엔계 라텍스의 제조방법으로 제조되는 스티렌-부타디엔계 라텍스를 제공한다.The present invention also provides a styrene-butadiene-based latex prepared by the method for producing the styrene-butadiene-based latex.
또한, 본 발명은 상기 스티렌-부타디엔계 라텍스의 제조방법으로 제조되는 스티렌-부타디엔계 라텍스를 포함하는 종이 코팅액 조성물을 제공한다.In addition, the present invention provides a paper coating liquid composition comprising a styrene-butadiene-based latex produced by the method for producing the styrene-butadiene-based latex.
또한, 본 발명은 상기 스티렌-부타디엔계 라텍스의 제조방법으로 제조되는 스티렌-부타디엔계 라텍스를 포함하는 종이 코팅액 조성물로 코팅 처리된 코팅 종이를 제공한다.The present invention also provides a coated paper coated with a paper coating liquid composition comprising a styrene-butadiene-based latex produced by the method for producing the styrene-butadiene-based latex.
또한, 본 발명은 스티렌-부타디엔계 라텍스에 있어서, 스티렌-부타디엔계 중합체의 코아 라텍스에 쉘 중합물로서 스티렌-부타디엔계 중합체가 상기 코아 라텍스의 외부에 다중으로 피복된 구조를 갖는 스티렌-부타디엔계 라텍스를 제공한다.In addition, the present invention provides a styrene-butadiene-based latex, in the styrene-butadiene-based latex, a styrene-butadiene-based latex having a structure in which a styrene-butadiene-based polymer is multi-coated outside the core latex as a shell polymer to provide.
이하, 본 발명에 대하여 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명의 스티렌-부타디엔계 라텍스는 다중 코아-쉘 중합 단계를 포함하며, 더욱 상세하게는 본 발명은 제 1 단계 중합으로 코아 제조단계, 및 제 2 단계 중합으로 코아에 다른 조성의 쉘을 다중으로 피복하여 다중 코아-쉘을 형성시키는 단계로 이루어지며, 각 공정은 유화중합에 의해 이루어진다. 이때 쉘은 1개 이상으로 제조할 수 있으며, 각 쉘은 유리전이온도, 겔 함량, 분자량 등을 고려하여 코아-쉘 구조를 이룰 수 있도록 설계하여야 하며, 바람직하게는 2∼4개가 적당하다. 제 3 단계는 다중 쉘 중합이 끝난 후 전환율이 60∼95%가 되는 시점에서 일정 시간 동안 연쇄이동제를 단독으로 일정량 투입하는 단계로써 라텍스 입자의 최외곽층의 겔 함량과 분자량을 조절하기 위하여 반드시 필요한 단계이다. 이때 투입량은 전체 투입 단량체 100 중량부에 대하여 0.05 ~ 5.0 중량부가 바람직하다.The styrene-butadiene-based latex of the present invention comprises a multiple core-shell polymerization step, and more particularly, the present invention relates to a core preparation step in a first step polymerization and a shell of a different composition to cores in a second step polymerization. Coating to form multiple core-shells, each process being carried out by emulsion polymerization. In this case, one or more shells may be manufactured, and each shell should be designed to achieve a core-shell structure in consideration of glass transition temperature, gel content, molecular weight, and the like, preferably 2 to 4 pieces. The third step is to inject a certain amount of the chain transfer agent alone for a predetermined time when the conversion rate is 60 to 95% after the completion of the multi-shell polymerization, which is essential for controlling the gel content and molecular weight of the outermost layer of the latex particles. Step. In this case, the amount is preferably 0.05 to 5.0 parts by weight based on 100 parts by weight of the total amount of the monomers.
상기 제 1 단계를 통하여 제조되는 코아는 최종 라텍스에 비해 적절한 겔 함량과 함께 적절한 친수도를 가지는 것이 특징이고, 제 2단계 중합에서는 적절한 유리전이온도와 쉬트 옵셋용인 경우 높은 겔 함량을, 웹 옵셋용인 경우 낮은 겔 함량을 갖는 것이 특징이다.The core prepared through the first step is characterized by having an appropriate hydrophilicity with an appropriate gel content compared to the final latex, and in the second stage polymerization, a high gel content is required for the appropriate glass transition temperature and sheet offset, and for web offset It is characterized by having a low gel content.
본 발명에 따른 스티렌-부타디엔계 라텍스의 제조방법을 하기에 더욱 상세하게 설명한다.The production method of the styrene-butadiene-based latex according to the present invention will be described in more detail below.
제 1 단계는 코아를 초기 중합하는 공정으로, 상기 코아의 조성은 스티렌 35 내지 90 중량부, 1,3-부타디엔 10 내지 55 중량부, 에틸렌성 불포화 산 단량체 1 내지 18 중량부, 및 시안화 비닐계 단량체 0.5 내지 15 중량부, 이들과 공중합이 가능한 단량체 1 내지 25 중량부, 및 연쇄이동제(chain transfer agent) 0.1 내지 1.0 중량부를 포함한다.The first step is the initial polymerization of the core, the composition of the core is 35 to 90 parts by weight of styrene, 10 to 55 parts by weight of 1,3-butadiene, 1 to 18 parts by weight of ethylenically unsaturated acid monomer, and vinyl cyanide 0.5 to 15 parts by weight of monomers, 1 to 25 parts by weight of monomers copolymerizable with these, and 0.1 to 1.0 parts by weight of a chain transfer agent.
상기 스티렌은 공중합체에 적절한 경도 및 내수성을 부여하는 물질로서, 단량체에 35 중량부 미만으로 포함될 경우 충분한 경도와 내수성을 수득할 수 없으며, 90 중량부를 초과할 경우에는 접착력 및 필름형성력이 저하된다.The styrene is a substance that imparts appropriate hardness and water resistance to the copolymer, and when included in the monomer at less than 35 parts by weight, sufficient hardness and water resistance cannot be obtained. When the styrene is more than 90 parts by weight, adhesion and film forming power are lowered.
상기 1,3-부타디엔은 공중합체에 유연성을 부여한다. 상기 1, 3-부타디엔이 10 중량부 미만일 경우에는 공중합체가 너무 단단해지고, 55 중량부를 초과할 경우는 강직성이 저하된다.The 1,3-butadiene imparts flexibility to the copolymer. When the said 1, 3- butadiene is less than 10 weight part, a copolymer becomes hard too much, and when it exceeds 55 weight part, rigidity will fall.
상기 에틸렌성 불포화 산 단량체는 공중합체의 접착력을 향상시키고 라텍스 입자의 안정성을 개선시키기 위하여 적절하게 사용된다. 상기 에틸렌성 불포화 산 단량체의 조성비는 1 내지 18 중량부가 바람직하며, 이 양이 1 중량부 미만이면 상기 효과를 수득할 수 없고, 18 중량부 초과하게 되면 중합안정성 등에 문제가 발생할 수 있다. 상기 에틸렌성 불포화 산 단량체는 불포화카르복실 산 또는 1개 이상의 카르복실기를 갖는 불포화 폴리카르복실산 알킬 에스테르가 바람직하다.The ethylenically unsaturated acid monomers are suitably used to improve the adhesion of the copolymer and to improve the stability of the latex particles. The composition ratio of the ethylenically unsaturated acid monomer is preferably 1 to 18 parts by weight, and if the amount is less than 1 part by weight, the above effects cannot be obtained. If the amount is more than 18 parts by weight, problems such as polymerization stability may occur. The ethylenically unsaturated acid monomer is preferably unsaturated carboxylic acid or unsaturated polycarboxylic acid alkyl ester having at least one carboxyl group.
상기 불포화카르복실 산은 메타크릴산, 아크릴산, 이타콘산, 크로톤산, 푸마르산, 및 말레인산으로 이루어진 군으로부터 1종 이상 선택되는 것이 바람직하며, 상기 불포화 폴리카르복실산 알킬 에스테르는 이타콘산 모노에틸 에스테르, 푸마르산 모노부틸 에스테르 및 말레산 모노부틸 에스테르로 이루어진 군으로부터 1종 이상 선택하는 것이 바람직하다. The unsaturated carboxylic acid is preferably selected from the group consisting of methacrylic acid, acrylic acid, itaconic acid, crotonic acid, fumaric acid, and maleic acid, wherein the unsaturated polycarboxylic acid alkyl ester is itaconic acid monoethyl ester, fumaric acid It is preferable to select at least one from the group consisting of monobutyl ester and maleic monobutyl ester.
상기 시안화 비닐계 단량체는 인쇄광택을 향상시키며 그 함량은 3 내지 10 중량부가 바람직하다. 또한 시안화 비닐계 단량체는 에틸렌성 불포화 산 단량체와 함께 높은 친수도를 가지므로 바람직한 함량내에서 조절하여 중합단계별 친수도를 조절하는 것이 바람직하다. 상기 시안화 비닐계 단량체는 아크릴로니트릴 또는 메타크릴로니트릴이 바람직하다.The vinyl cyanide monomer improves printing glossiness, and its content is preferably 3 to 10 parts by weight. In addition, since the vinyl cyanide monomer has a high hydrophilicity together with the ethylenically unsaturated acid monomer, it is preferable to control the hydrophilicity according to the polymerization step by controlling within the desired content. The vinyl cyanide monomer is preferably acrylonitrile or methacrylonitrile.
상기 공중합이 가능한 단량체는 메틸아크릴레이트, 메틸메타크릴레이트, 에틸아크릴레이트, 에틸메타크릴레이트, 부틸아크릴레이트, 부틸메타크릴레이트 등과 같은 불포화 카르복실산 알킬 에스테르; β-히드록시에틸 아크릴레이트, β-히드록시프로필 아크릴레이트 및 β-히드록시에틸 메타크릴레이트 같은 불포화카르복실산 히드록시알킬 에스테르; 아크릴아미드, 메타크릴아미드, 이타콘아미드, 말레산모노아미드 같은 불포화 카르복실산 아미드 및 그 유도체; 및 α-메틸스티렌, 비닐톨루엔, P-메틸스티렌 같은 방향족 비닐 단량체로 이루어진 군으로부터 1 종 이상 선택되는 것이 바람직하다. 상기 불포화 카르복실산 알킬 에스테르는 공중합체에 적당한 경도를 부여하고 필름형성력을 향상시키며, 함량이 25 중량부를 초과하면 내수성에 좋지 못한 영향을 초래하므로 3 내지 15 중량부인 것이 더욱 바람직하다. 또한 상기 불포화 카르복실산 아미드 및 그 유도체는 공중합체 라텍스의 화학적 안정성, 기계적 안정성 및 내수성을 개선하는 효과를 가지며 함량은 1 내지 10 중량부가 더욱 바람직하다.The copolymerizable monomers include unsaturated carboxylic acid alkyl esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate and butyl methacrylate; unsaturated carboxylic hydroxyalkyl esters such as β-hydroxyethyl acrylate, β-hydroxypropyl acrylate and β-hydroxyethyl methacrylate; Unsaturated carboxylic acid amides and derivatives thereof such as acrylamide, methacrylamide, itaconeamide, maleic acid monoamide; And aromatic vinyl monomers such as α-methylstyrene, vinyltoluene, and P-methylstyrene. The unsaturated carboxylic acid alkyl ester is more preferably 3 to 15 parts by weight to impart proper hardness to the copolymer and improve film forming ability, and if the content exceeds 25 parts by weight, it will adversely affect the water resistance. In addition, the unsaturated carboxylic acid amide and its derivatives have the effect of improving the chemical stability, mechanical stability and water resistance of the copolymer latex, the content is more preferably 1 to 10 parts by weight.
본 발명에서 사용된 연쇄이동제는 탄소원자수 7~16개의 머캅탄으로 이루어진 군으로부터 선택하는 것이 바람직하며, n-도데실 머캅탄, t-도데실 머캅탄이 선택되어 지는 것이 더욱 바람직하다.The chain transfer agent used in the present invention is preferably selected from the group consisting of mercaptans having 7 to 16 carbon atoms, and more preferably n-dodecyl mercaptan and t-dodecyl mercaptan are selected.
본 발명의 코아 제조는 상기 코아 조성물에 일반적인 중합개시제, 유화제, 전해질 등의 첨가제의 첨가 하에 통상의 유화 중합반응으로 실시한다.The core preparation of the present invention is carried out by the usual emulsion polymerization reaction under the addition of additives such as general polymerization initiator, emulsifier, electrolyte and the like to the core composition.
본 발명의 라텍스 코아는 겔함량이 80 중량% 이하가 되는 것이 바람직하며, 특히 40 내지 70 중량%이다. 코아의 겔 함량이 80 중량%를 초과하는 경우에는 코아 제조단계 이후의 제 2 단계 이상의 중합에서 구조조절이 어려워져 다중 코아-쉘 구조를 형성하기가 어렵다.The latex core of the present invention preferably has a gel content of 80% by weight or less, in particular 40 to 70% by weight. If the gel content of the core exceeds 80% by weight, it is difficult to control the structure in the second or more polymerization after the core manufacturing step, making it difficult to form a multi core core-shell structure.
본 발명의 라텍스 제조단계 중 제 2단계는 상기 제 1 단계에서 제조된 코아 라텍스 위에 쉘을 피복하는 단계이다. 쉘 조성물은 스티렌 30 내지 80 중량부, 1,3-부타디엔 10 내지 70 중량부, 에틸렌성 불포화 산 단량체 0.5 내지 18 중량부, 연쇄이동제 0.1 내지 5.0 중량부를 포함한다. 또한 시안화 비닐계 단량체 1.0 내지 20 중량부, 및 다른 단량체와 중합 가능한 기타 단량체 1.0 내지 20 중량부를 포함할 수 있다.The second step of the latex manufacturing step of the present invention is a step of coating the shell on the core latex prepared in the first step. The shell composition comprises 30 to 80 parts by weight of styrene, 10 to 70 parts by weight of 1,3-butadiene, 0.5 to 18 parts by weight of ethylenically unsaturated acid monomer, and 0.1 to 5.0 parts by weight of the chain transfer agent. It may also include 1.0 to 20 parts by weight of vinyl cyanide monomer, and 1.0 to 20 parts by weight of other monomers polymerizable with other monomers.
본 발명의 제 2 단계에서 제조된 다중 쉘은 겔 함량이 30 내지 90 중량%으로 되는 것이 바람직하고, 쉬트 옵셋용인 경우 60 내지 85 중량%, 웹 옵셋용인 경우 40 내지 60 중량%인 것이 더욱 바람직하다. 쉬트 옵셋용인 경우 제 2 단계에서 제조된 쉘의 상기 겔 함량이 60 중량% 미만일 경우는 접착력, 잉크건조속도와 라텍스의 안정성이 저하되며 85 중량% 이상인 경우 또한 접착력을 확보하기가 어렵다. 또한 웹 옵셋용인 경우 제 2 단계에서 제조된 쉘의 상기 겔 함량이 20 중량% 미만일 경우는 접착력과 라텍스의 안정성이 저하될 수 있으며, 겔 함량이 70 중량%를 초과하면 내블리스터 특성이 저하된다.The multi-shell prepared in the second step of the present invention preferably has a gel content of 30 to 90% by weight, more preferably 60 to 85% by weight for sheet offset and 40 to 60% by weight for web offset. . In the case of sheet offset, when the gel content of the shell prepared in the second step is less than 60% by weight, the adhesion strength, the ink drying speed, and the stability of the latex are lowered. In addition, in the case of the web offset, when the gel content of the shell prepared in the second step is less than 20% by weight, the adhesive strength and the stability of the latex may be reduced, and when the gel content exceeds 70% by weight, the blister resistance is deteriorated. .
본 발명의 라텍스 제조단계 중 제 2단계인 다중 코아-쉘은 전단계에서 단량체의 고분자로의 전환율이 55 내지 95 % 수준일 때 새로운 단량체 혼합물을 투입하여 중합함으로써 제조한다. 전단계의 고분자로의 전환율이 55 % 미만이면 전단계의 단량체와 다음 단계 쉘의 단량체가 혼재되어 구조가 확실히 분리되지 않으므로 효과적인 다중 코아-쉘 구조를 얻기가 어렵다.The second core of the latex manufacturing step of the present invention is a multi-core shell is prepared by the polymerization of a new monomer mixture when the conversion of the monomer to the polymer at the level of 55 to 95% in the previous step. If the conversion rate to the polymer of the previous stage is less than 55%, it is difficult to obtain an effective multiple core-shell structure because the structure of the monomer of the previous stage and the monomer of the next stage are mixed so that the structure is not separated.
상기 2 단계에서 사용될 수 있는 각각의 단량체는 1 단계의 코아 제조 단계에서 사용되는 원료와 동일한 것을 사용한다.Each monomer that can be used in the second step is the same as the raw material used in the core preparation step of step 1.
본 발명의 라텍스의 제조단계는 최종 쉘 중합을 위한 단량체들의 투입되어 다중 쉘 중합 단계가 끝난 후 일정 시간 동안 일정량의 연쇄이동제를 단독으로 투입하는 단계를 포함하며, 이 단계는 최종 라텍스의 겔 함량 및 분자량 조절을 위하여 매우 중요한 단계이다. 최종 쉘 중합을 위한 단량체들의 투입이 끝난 후 전환율은 60 내지 95 %가 적당하며, 전환율 60% 미만이나 95%이상에서는 투입한 연쇄이동제를 통한 최외곽층의 겔 함량 및 분자량 조절 효과를 발휘하기 어렵다. 투입시간은 최종 쉘 중합을 위한 단량체들의 투입이 끝난 직후부터 2시간 동안이 바람직하며, 더욱 바람직하게는 투입이 끝난 직후부터 1시간이 바람직하다. 상기 연쇄이동제의 투입량은 0.05 내지 5.0 중량부가 바람직하며, 더욱 바람직하게는 0.1 내지 1.0 중량부이다.The step of preparing the latex of the present invention comprises the step of adding a predetermined amount of the chain transfer agent alone for a predetermined time after the completion of the multi-shell polymerization step of the monomers for the final shell polymerization, this step is the gel content of the final latex and This is a very important step for molecular weight control. After the addition of the monomers for the final shell polymerization, the conversion rate is suitable to 60 to 95%, and the conversion rate of the outermost layer through the added chain transfer agent is less than 60% or more than 95%, it is difficult to achieve the effect of controlling the gel content and molecular weight . The addition time is preferably 2 hours from the end of the addition of the monomers for the final shell polymerization, more preferably 1 hour from the end of the addition. The amount of the chain transfer agent is preferably 0.05 to 5.0 parts by weight, more preferably 0.1 to 1.0 part by weight.
또한 본 발명의 라텍스는 제조과정 중 다중 쉘을 중합하는 제 2 단계에서 각 쉘의 두께와 유리전이온도를 적합하게 제조하는 것이 중요하다. 각 쉘의 두께는 코아의 함량 및 단량체 함량을 조절함으로써 제어할 수 있으며, 이를 적절하게 제어하지 않으면 바람직한 구조의 라텍스를 얻을 수 없다. 또한 각 공정에서의 유리전이온도, 겔 함량, 분자량을 적절하게 제어함으로써 접착력, 잉크건조속도, 라텍스의 안정성 등의 물성을 효과적으로 조절할 수 있다.In addition, it is important that the latex of the present invention suitably prepares the thickness and glass transition temperature of each shell in the second step of polymerizing multiple shells during the manufacturing process. The thickness of each shell can be controlled by adjusting the core content and the monomer content, and if it is not properly controlled, latex of the desired structure cannot be obtained. In addition, by appropriately controlling the glass transition temperature, gel content, molecular weight in each process, physical properties such as adhesion strength, ink drying speed, and latex stability can be effectively controlled.
본 발명의 라텍스의 제조과정 중 적합한 두께는 제 1 단계의 코아 중합 후 평균 입경이 40 내지 90 nm이 바람직하고, 최종 쉘 중합 후 적합한 평균 입경은 110 내지 260 nm가 바람직하다.The suitable thickness during the preparation of the latex of the present invention is preferably 40 to 90 nm in average particle size after core polymerization in the first step, and preferably 110 to 260 nm in average particle diameter after final shell polymerization.
또한, 본 발명의 라텍스의 제조과정 중 적합한 유리전이 온도는 제 1 단계 시드의 유리전이온도는 -10 내지 50 ℃가 바람직하고, 다중 쉘의 유리전이온도는 -20 내지 40 ℃가 바람직하다.In addition, the glass transition temperature of the first stage seed during the manufacturing process of the latex of the present invention is preferably -10 to 50 ℃, the glass transition temperature of the multiple shell is preferably -20 to 40 ℃.
본 발명의 스티렌-부타디엔계 라텍스는 유,무기안료, 증점제, 기타 첨가제와 혼합하여 수성 코팅액을 제조할 수 있으며, 상기 코팅액을 코팅지에 코팅함으로써 코팅지를 제조할 수 있다. 상기 무기안료는 일반적인 산화티탄, 탄산칼슘, 클레이 등의 안료 및 익스텐더(pigment extender) 등이며, 라텍스의 함유량은 수성 코팅액의 고형분 100 중량부에 대하여 5 내지 20 중량부가 바람직하다.Styrene-butadiene-based latex of the present invention can be mixed with organic, inorganic pigments, thickeners, and other additives to prepare an aqueous coating solution, it is possible to produce a coating paper by coating the coating solution on the coating paper. The inorganic pigment is a pigment such as titanium oxide, calcium carbonate, clay, extender, etc., and the content of latex is preferably 5 to 20 parts by weight based on 100 parts by weight of the solid content of the aqueous coating solution.
이하, 하기의 실시예를 통하여 본 발명을 더욱 상세히 설명하지만, 본 발명의 범위가 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the examples.
[실시예 1 내지 7][Examples 1 to 7]
본 발명의 스티렌-부타디엔계 라텍스를 하기와 같이 3 단계로 제조하였다.Styrene-butadiene-based latex of the present invention was prepared in three steps as follows.
제 1 단계: 코아 제조 단계First step: core manufacturing step
교반기, 온도계, 냉각기, 질소가스의 인입구가 설치되어 있으며, 단량체, 유화제 및 중합반응 개시제를 연속적으로 투입할 수 있도록 장치된 10 L 가압 반응기를 질소로 치환한 후, 부타디엔 33 중량부, 스티렌 49 중량부, 메틸메타크릴레이트 8 중량부, 아크릴로니트릴 5 중량부, 이타콘산 5 중량부, 도데실 디벤젠 술폰산 나트륨 6 중량부, t-도데실머캅탄 0.3 중량부, 나트륨 바이카보네이트 0.4 중량부, 이온교환수 420 중량부를 넣은 다음 60 ℃까지 승온하였다. 여기에 중합개시제인 칼륨퍼설페이트를 0.8 중량부 넣고 약 300분간 교반하여 시드의 중합을 완료시켰다.A stirrer, a thermometer, a cooler, and an inlet for nitrogen gas are installed, and after replacing a 10 L pressurized reactor equipped with nitrogen, a monomer, an emulsifier and a polymerization initiator continuously, 33 parts by weight of butadiene and 49 parts of styrene Part, 8 parts by weight of methyl methacrylate, 5 parts by weight of acrylonitrile, 5 parts by weight of itaconic acid, 6 parts by weight of sodium dodecyl dibenzene sulfonate, 0.3 parts by weight of t-dodecylmercaptan, 0.4 parts by weight of sodium bicarbonate, and 420 parts by weight of exchanged water was added, and the temperature was raised to 60 ° C. 0.8 parts by weight of potassium persulfate as a polymerization initiator was added thereto, followed by stirring for about 300 minutes to complete polymerization of the seed.
상기 코아는 레이저 분산분석기(Laser Scattering Analyzer, Nicomp)로 측정한 결과 평균 입경은 68 nm였고, 겔 함량은 53 %, 전환율은 97 %이었다.The core was measured by a laser scattering analyzer (Nicomp), the average particle diameter was 68 nm, gel content was 53%, conversion was 97%.
제 2 단계: 다중 쉘 제조 단계Second Step: Multiple Shell Manufacturing Steps
상기 제 1 단계에서 얻어진 코아에 쉘을 피복시키기 위하여 반응기에 코아 라텍스 8중량부와 이온 교환수 30 중량부를 다시 채우고 80 ℃까지 승온한 후, 적절한 조성의 쉘 조성물을 투입하여 유화중합을 통하여 제조하였으며, 실시예 1∼2는 쉘의 개수 2개로, 실시예 3∼7은 쉘의 개수 3개로 제조하였다. 이때 투입된 쉘 조성물의 단량체 합은 100이며, 성분들이 모두 투입된 후 전환율은 70 내지 90 %였다.In order to coat the core with the core obtained in the first step, 8 parts by weight of core latex and 30 parts by weight of ion-exchanged water were refilled in the reactor, and the temperature was raised to 80 ° C. , Examples 1 to 2 were manufactured by the number of shells, and Examples 3 to 7 were manufactured by the number of shells. At this time, the monomer sum of the introduced shell composition was 100, and the conversion rate was 70 to 90% after all the components were added.
제 3 단계: 최외곽층 겔 함량 및 분자량 조절 단계Third Step: Control of Outer Layer Gel Content and Molecular Weight
제 2 단계에서 얻어진 라텍스에 연쇄이동제를 단독으로 투입하여 최외곽층의 겔 함량 및 분자량을 조절하기 위하여 제 2 단계가 채워져 있는 반응기의 온도를 80 ℃로 유지시킨 후, 상기 표 1 제 3 단계의 성분을 30 분 동안 연속 투입하여 중합한다.In order to control the gel content and molecular weight of the outermost layer by adding a chain transfer agent to the latex obtained in the second step alone, the temperature of the reactor filled with the second step was maintained at 80 ° C., The ingredients are polymerized by continuous feeding for 30 minutes.
또한 실시예 6∼9는 제 2 단계에서 두번째 쉘 제조 후 30분간 상기 표 1의 성분을 단독으로 투입한 후 세번째 쉘을 제조하고, 이 후 제 3 단계를 진행하였다.In addition, Examples 6 to 9 were prepared by injecting the components of Table 1 alone for 30 minutes after preparing the second shell in the second step, and then preparing a third shell, and then proceeding to the third step.
상기 성분들이 모두 투입한 다음 90 ℃까지 승온하여 반응을 촉진시키면서 100 분간 추가 교반하여 중합을 완료하였다. 중합이 완료된 라텍스의 전환율은 98 내지 100 %였으며, 평균입경은 180 nm로 측정되었다. After all the ingredients were added, the temperature was raised to 90 ° C., further stirring for 100 minutes while promoting the reaction to complete the polymerization. The conversion of the latex polymerized was 98 to 100%, and the average particle diameter was measured at 180 nm.
[비교예 1]Comparative Example 1
실시예 1∼2의 제 1, 2 단계와 동일한 방법으로 쉘의 개수가 2개인 코아-쉘 라텍스를 제조하였으며, 최종 겔 함량을 실시예와 같은 정도로 맞추기 위하여 제 3 단계가 없는 대신 제 2 단계의 쉘 제조시 연쇄이동제의 양을 조절하였다. Core-shell latexes having two shells were prepared in the same manner as in the first and second steps of Examples 1 and 2, and in order to adjust the final gel content to the same degree as in Example, there was no third step but instead of the second step. The amount of chain transfer agent was adjusted during shell preparation.
[비교예 2]Comparative Example 2
실시예 3∼5의 제 1, 2 단계와 동일한 방법으로 쉘의 개수가 3개인 코아-쉘 라텍스를 제조하였으며, 비교예 1과 마찬가지로 최종 겔 함량을 실시예와 같은 정도를 맞추기 위하여 제 2 단계의 쉘 제조시 연쇄이동제의 양을 조절하였다. Core-shell latexes having three shells were prepared in the same manner as in the first and second steps of Examples 3 to 5, and in the same manner as in Comparative Example 1, the final gel content was adjusted in the same manner as in the second step. The amount of chain transfer agent was adjusted during shell preparation.
[비교예 3 내지 6][Comparative Examples 3 to 6]
실시예 6∼9의 제 1, 2 단계와 동일한 방법으로 쉘의 개수가 3개인 코아-쉘 라텍스를 제조하였으며, 이때 실시예 6∼9와 마찬가지로 두번째 쉘 제조 후, 단독으로 연쇄이동제를 하기 표 2와 같이 30분간 투입한 후 세번째 쉘을 제조하였다. 역시 최종 겔 함량을 실시예와 같은 정도를 맞추기 위하여 제 2 단계의 쉘 제조시 연쇄이동제의 양을 조절하였다.In the same manner as in the first and second steps of Examples 6 to 9, a core-shell latex having three shells was prepared. In this case, as in Examples 6 to 9, after the second shell was manufactured, a chain transfer agent was independently added. After the 30 minutes were added to prepare a third shell. In order to adjust the final gel content to the same degree as in Example, the amount of chain transfer agent was adjusted during the shell preparation in the second step.
[실시예 8] Example 8
라텍스의 기계적 안정성을 측정하기 위하여 라텍스를 단독으로 마론 테스터(Maron tester)를 사용하여 측정하였으며, 화학적, 기계적 안정성을 동시에 측정하기 위하여 라텍스와 인조안료를 혼합한 코팅 조성물(하기 실시예 9 참조)을 제조한 후 마론 테스터(Maron tester)를 사용하여 측정하였다. 안정성의 측정 실험 결과는 마론 테스터(Maron tester) 완료 후 라텍스 및 코팅조성물을 325 mesh로 걸러서 응고물을 ppm 단위로 측정하였다.In order to measure the mechanical stability of the latex was measured using a Maron tester (Maron tester) alone, in order to simultaneously measure the chemical and mechanical stability of the coating composition mixed with a latex and artificial pigment (see Example 9 below) After the preparation was measured using a Maron tester (Maron tester). Measurement of stability Experimental results were measured after the completion of the Maron tester (Maron tester) by filtering the latex and coating composition with a 325 mesh coagulation in ppm unit.
[실시예 9]Example 9
실시예 및 비교예의 라텍스를 비교, 평가하기 위하여 고형분을 기준으로 하여 기준 클레이(1급) 30 중량부, 탄산칼슘 70 중량부, 라텍스 12 중량부, 증점제 0.8 중량부, 기타 첨가제 1.2 중량부로 고형분 64 중량%의 종이 코팅액을 제조하였다. 제조된 종이 코팅액은 로드 수동 양면 코팅(Rod Coating, No 7)으로 코팅지 양면을 각 15 g/m2 코팅한 다음 105 ℃에서 30초간 건조시킨 다음 슈퍼칼렌다에 80 ℃에서 40 kg/cm 하에서 2회 통과(통과속도: 4 m/min)시켜 코팅지를 제조하였다. In order to compare and evaluate the latex of the Examples and Comparative Examples, based on the solid content, 30 parts by weight of the reference clay (grade 1), 70 parts by weight of calcium carbonate, 12 parts by weight of latex, 0.8 parts by weight of thickener, 1.2 parts by weight of other additives, 64 A weight% paper coating solution was prepared. The prepared paper coating solution was rod coated (Rod Coating, No 7), coated on both sides of coated paper at 15 g / m2, dried at 105 ° C for 30 seconds, and then passed through a super calender at 40 ° C / cm at 80 ° C twice. (Paneling speed: 4 m / min) to prepare a coated paper.
상기에서 제조한 코팅지의 물성으로 접착력, 잉크건조속도 및 투기도를 측정하였다. 측정 방법은 하기에 나타내었고 결과는 표 4에 기재하였다.The adhesion, ink drying speed and air permeability were measured by the properties of the coated paper prepared above. The measurement method is shown below and the results are shown in Table 4.
접착력은 코팅지를 RI 인쇄기에서 수회에 걸쳐 인쇄한 후 뜯김의 정도를 육안으로 판정하여 5 점법으로 평가했다. 점수가 높을수록 접착력이 양호함을 나타내며, 태크밸류 12, 14, 16의 잉크를 각각 사용하여 측정한 후, 평균치를 구하였다.Adhesive force was evaluated by the 5-point method by visually determining the degree of tearing after printing coated paper several times on an RI printing machine. The higher the score, the better the adhesion. After the measurement using the inks of Tack Values 12, 14 and 16, respectively, the average value was obtained.
잉크건조속도는 코팅지를 RI 인쇄기에서 인쇄한 후, 시간에 따라 잉크가 묻어나오는 정도를 5점법으로 측정하였다. 점수가 높을수록 잉크건조속도가 빠른 것을 의미한다.The ink drying speed was measured by the five-point method after the coated paper was printed on the RI printing machine, the degree of ink out with time. The higher the score, the faster the ink drying speed.
투기도는 OKEN 포로시미터(porosimeter) 측정 장치로 코팅지의 여러 부분을 측정하여 평균치를 구하였으며, 수치는 단위 부피의 공기가 코팅지를 통과하는데 걸리는 시간을 의미한다. 수치가 작을수록 공기 통과가 빠른 것을 의미하며 그만큼 코팅층의 투기도가 양호함을 나타낸다. 단위는 초(second)이다.The air permeability was averaged by measuring various parts of the coated paper with an OKEN porosimeter measuring device, and the value means the time taken for the unit volume of air to pass through the coated paper. The smaller the value, the faster the air passage and the better the air permeability of the coating layer. The unit is second.
상기 표 4와 같이 코팅액 및 코팅지 물성과 인쇄물성을 측정한 결과, 실시예 1∼2의 2중 코아-쉘 구조의 라텍스가 2중 쉘 제조 후, 연쇄이동제의 투입이 없는 비교예 1에 비해 접착력이 우수하고 잉크건조속도 및 투기도 특성이 뛰어났으며, 마찬가지로 쉘의 제조 후 연쇄이동제를 단독으로 투입하여 최외곽층의 겔 함량과 분자량을 조절한 실시예 3∼6의 3중 코아-쉘 구조의 라텍스가 비교예 2의 3중 코아-쉘 구조 라텍스에 비하여 뛰어난 접착력과 매우 우수한 잉크건조속도 및 투기도 특성을 보이는 결과를 얻을 수 있었다.As a result of measuring the coating liquid and the coated paper physical properties and printability as shown in Table 4, after the double shell production of the double core-shell structure of Examples 1 to 2, the adhesive strength compared to Comparative Example 1 without the addition of a chain transfer agent It has excellent ink drying speed and air permeability, and similarly, the triple core-shell structure of Examples 3 to 6 in which the chain transfer agent was added alone to control the gel content and molecular weight of the outermost layer after the shell was prepared. Compared to the triple core-shell structured latex of Comparative Example 2, the latex was able to obtain excellent adhesive strength and very good ink drying speed and air permeability characteristics.
3중 쉘을 피복하는 과정에서 두번째 쉘을 피복한 후 연쇄이동제를 단독으로 투입하여 쉘 제조 도중 겔 함량과 분자량을 조절한 비교예 3∼6의 경우 비교예 2에 비해 잉크건조속도와 투기도는 다소 향상되나 전반적으로 그다지 우수한 물성을 얻을 수 없었으며 실시예 6∼9의 경우처럼 마지막 세번째 쉘 제조 후 연쇄이동제를 단독으로 투입하여 최외곽층의 겔 함량 및 분자량을 조절한 경우에 우수한 접착력과 잉크건조속도 및 투기도를 얻을 수 있었다.In the case of coating the triple shell, the drying rate and the air permeability of Comparative Examples 3 to 6, in which the gel content and the molecular weight were adjusted during shell production by coating the second shell and then adding the chain transfer agent alone, were compared with those of Comparative Example 2. Although slightly improved, overall excellent physical properties were not obtained, and excellent adhesion and ink when the gel content and molecular weight of the outermost layer were adjusted by adding a chain transfer agent alone after the final third shell production, as in the case of Examples 6 to 9 Drying rate and air permeability were obtained.
본 발명에 따른 스티렌-부타디엔계 라텍스는 최외곽층의 겔 함량 및 분자량을 조절함으로써 코팅시 초기 필름 형성을 빠르게 하여 라텍스의 접착 능력을 뛰어나며 적절한 필름 형성을 유지하여 잉크건조속도가 빠르고 투기도가 높다는 특성을 지니며 라텍스의 기계적, 화학적 안정성이 탁월하여 종이 코팅에 매우 안정적으로 적용할 수 있다.Styrene-butadiene-based latex according to the present invention by controlling the gel content and molecular weight of the outermost layer to accelerate the initial film formation during coating, excellent adhesion ability of the latex, maintaining the proper film formation, ink drying speed is fast and high air permeability It has the characteristics and excellent mechanical and chemical stability of latex, so it can be applied to paper coating very stably.
상기에서 본 발명은 기재된 구체예를 중심으로 상세히 설명되었지만, 본 발명의 범주 및 기술사상 범위 내에서 다양한 변형 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.While the invention has been described in detail above with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the invention, and such modifications and variations fall within the scope of the appended claims. It is also natural.
Claims (17)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2003-0042582A KR100512366B1 (en) | 2003-06-27 | 2003-06-27 | Method for Preparing Styrene-Butadienes Latex |
| PCT/KR2004/000279 WO2005105898A1 (en) | 2003-06-27 | 2004-02-12 | Method of manufacture of styrene-butadiene latexes |
| CA 2530691 CA2530691C (en) | 2003-06-27 | 2004-02-12 | Method of manufacture of styrene-butadiene latexes |
| US10/553,586 US9040118B2 (en) | 2003-06-27 | 2004-02-12 | Method of manufacture of styrene-butadiene latexes |
| JP2006508517A JP2006526681A (en) | 2003-06-27 | 2004-02-12 | Method for producing styrene-butadiene latex |
| CNB2004800129337A CN100396718C (en) | 2003-06-27 | 2004-02-12 | Method of manufacture of styrene-butadiene latexes |
| EP20040821822 EP1639031B1 (en) | 2003-06-27 | 2004-02-12 | Method of manufacture of styrene-butadiene latexes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2003-0042582A KR100512366B1 (en) | 2003-06-27 | 2003-06-27 | Method for Preparing Styrene-Butadienes Latex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20050004949A KR20050004949A (en) | 2005-01-13 |
| KR100512366B1 true KR100512366B1 (en) | 2005-09-02 |
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| Application Number | Title | Priority Date | Filing Date |
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| KR10-2003-0042582A KR100512366B1 (en) | 2003-06-27 | 2003-06-27 | Method for Preparing Styrene-Butadienes Latex |
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| Country | Link |
|---|---|
| US (1) | US9040118B2 (en) |
| EP (1) | EP1639031B1 (en) |
| JP (1) | JP2006526681A (en) |
| KR (1) | KR100512366B1 (en) |
| CN (1) | CN100396718C (en) |
| CA (1) | CA2530691C (en) |
| WO (1) | WO2005105898A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101041304B1 (en) * | 2006-12-07 | 2011-06-14 | 재단법인서울대학교산학협력재단 | Styrene-butadiene-based latex for inkjet paper binders, preparation method thereof and coating solution containing same |
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| WO2007027037A1 (en) | 2005-08-31 | 2007-03-08 | Lg Chem, Ltd. | Odorless paper coating latex and paper coating composition containing the same |
| KR100796149B1 (en) * | 2006-07-20 | 2008-01-21 | 주식회사 엘지화학 | Odorless paper latex |
| DE102005044521A1 (en) * | 2005-09-16 | 2007-03-22 | Basf Ag | Process for coating surfaces and suitable particles |
| US8674000B2 (en) | 2006-10-24 | 2014-03-18 | Lg Chem, Ltd. | Multi-layered paper coating latex having high swelling and contraction property, method for preparing the same, and paper coating composition containing the same |
| WO2008069538A1 (en) * | 2006-12-07 | 2008-06-12 | Lg Chem, Ltd. | Styrene-butadiene latex binder for ink-jet paper, preparation method thereof and coating liquid containing the same |
| KR101121050B1 (en) * | 2008-03-27 | 2012-03-15 | 주식회사 엘지화학 | Latex for paper coating with excellent adhesion and white gloss |
| KR20100083064A (en) | 2009-01-12 | 2010-07-21 | (주) 아이티비엠지 | System for providing interactive contents service in cable broadcasting environment |
| CN102020749B (en) * | 2009-09-15 | 2013-09-04 | Lg化学株式会社 | Multilayer rubber copolymer with excellent bleaching-resistant property and preparation method thereof |
| JP2016507623A (en) * | 2013-02-06 | 2016-03-10 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Hybrid latex containing polymer particles having a core-shell structure and method for producing the same |
| KR101442412B1 (en) * | 2013-05-03 | 2014-09-17 | 주식회사 엘지화학 | Rubbery polymer for rubber reinforced graft copolymer and method of preparing the same |
| KR101666273B1 (en) * | 2014-06-13 | 2016-10-24 | 주식회사 엘지화학 | Styrene-butadiene latex and preparation method thereof |
| EP3197947A4 (en) * | 2014-09-23 | 2018-05-09 | Bridgestone Bandag, LLC | Carbon black pellets bound by styrene-butadiene latex polymer |
| CN105820284B (en) * | 2016-04-28 | 2018-01-30 | 浙江天晨胶业股份有限公司 | A kind of preparation method of lawn polymeric latex |
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| CN110483673B (en) * | 2019-07-18 | 2022-04-15 | 广东腾龙化工科技有限公司 | Multiphase-structure styrene-butadiene latex for paper coating and preparation method and application thereof |
| CN110483676B (en) * | 2019-07-18 | 2022-04-15 | 广东腾龙化工科技有限公司 | A kind of heterophasic structure butadiene-styrene copolymer latex and its preparation method and application |
| CN115044331B (en) * | 2021-03-09 | 2023-05-09 | 南京工业大学 | A kind of water-dispersed polymer microparticle emulsion binder for lithium ion battery and preparation method thereof |
| CN113831439A (en) * | 2021-11-02 | 2021-12-24 | 上海昶法新材料有限公司 | A kind of carboxylated nitrile latex for papermaking and preparation method thereof |
| CN118562207B (en) * | 2024-08-01 | 2024-11-05 | 潍坊蓝励新材料有限公司 | A kind of environmentally friendly styrene-butadiene latex with enhanced viscosity and preparation method thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3970629A (en) * | 1972-08-07 | 1976-07-20 | Sumitomo Naugatuck Co., Ltd. | Composition for paper coating |
| US4331738A (en) | 1980-12-04 | 1982-05-25 | The General Tire & Rubber Company | Blend of a carboxylated copolymer latex and of an acrylate copolymer latex for coating rubber and product |
| JPS62117897A (en) | 1985-11-12 | 1987-05-29 | ジェイエスアール株式会社 | Paper coating composition |
| GB8821310D0 (en) * | 1988-09-12 | 1988-10-12 | Dow Chemical Co | Process for production of high molecular weight copolymers of diallyl dimethyl ammonium chloride & acrylamide in solution |
| KR100278934B1 (en) | 1992-01-10 | 2001-01-15 | 고마쓰바라 히로유끼 | Copolymer latex production method and its use |
| JPH0790798A (en) | 1993-09-20 | 1995-04-04 | New Oji Paper Co Ltd | Method for producing cast coated paper |
| US5770303A (en) * | 1994-07-06 | 1998-06-23 | Gencorp Inc. | Occluded composite-particle latex |
| US5585184A (en) * | 1994-09-29 | 1996-12-17 | Union Carbide Chemicals & Plastics Technology Corporation | Colorable non-sticky resin core-shell particles |
| CA2407152A1 (en) * | 2000-06-02 | 2001-12-13 | Dow Global Technologies Inc. | Monovinylidene aromatic polymers with improved toughness and rigidity and a process for their preparation |
| KR100405308B1 (en) | 2000-12-18 | 2003-11-12 | 주식회사 엘지화학 | Artificial pigment and method for preparing the same |
| KR100409076B1 (en) * | 2000-12-20 | 2003-12-11 | 주식회사 엘지화학 | Method for preparing latex in use paper coating |
-
2003
- 2003-06-27 KR KR10-2003-0042582A patent/KR100512366B1/en active IP Right Grant
-
2004
- 2004-02-12 EP EP20040821822 patent/EP1639031B1/en not_active Expired - Lifetime
- 2004-02-12 JP JP2006508517A patent/JP2006526681A/en active Pending
- 2004-02-12 WO PCT/KR2004/000279 patent/WO2005105898A1/en active Search and Examination
- 2004-02-12 CN CNB2004800129337A patent/CN100396718C/en not_active Expired - Lifetime
- 2004-02-12 CA CA 2530691 patent/CA2530691C/en not_active Expired - Lifetime
- 2004-02-12 US US10/553,586 patent/US9040118B2/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101041304B1 (en) * | 2006-12-07 | 2011-06-14 | 재단법인서울대학교산학협력재단 | Styrene-butadiene-based latex for inkjet paper binders, preparation method thereof and coating solution containing same |
Also Published As
| Publication number | Publication date |
|---|---|
| US20060263602A1 (en) | 2006-11-23 |
| CN1788039A (en) | 2006-06-14 |
| JP2006526681A (en) | 2006-11-24 |
| CA2530691C (en) | 2010-08-03 |
| KR20050004949A (en) | 2005-01-13 |
| CA2530691A1 (en) | 2005-11-10 |
| EP1639031B1 (en) | 2012-05-23 |
| EP1639031A4 (en) | 2006-07-12 |
| US9040118B2 (en) | 2015-05-26 |
| CN100396718C (en) | 2008-06-25 |
| WO2005105898A1 (en) | 2005-11-10 |
| EP1639031A1 (en) | 2006-03-29 |
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